Dielectric ceramic compositions

ABSTRACT

The present invention is directed to a dielectric ceramic composition composed of, 97.5 to 99.95 wt. % of main component represented by, {100-(a+b+c+d)} (Ba 100-x  Pb x ) TiO 3  +aZnO+bBi 2  O 3  +cNb 2  O 5  +dRe 2  O 3  (0.5≦a≦4.5, 0.5≦b≦4.5, 0.5≦c≦4.5, 0.5≦d≦5.5 and 0&lt;x≦6.0, and 0.05 to 2.5 wt. % of first by-component consisting of glass whose main component is SiO 2 . Also, the present invention is directed to a dielectric ceramic composition composed of main component represented by, {100-(a+b+c+d+e)} BaTiO 3  +aZnO+bBi 2  O 3  +cMeO 2  +dNb 2  O 5  +eRe 2  O 3  (0.5≦a≦4.5, 2.0≦b≦6.0, 0.5≦c≦6.5, 0.5≦d≦4.5 and 0.5≦e≦5.5), and first by-component. Furthermore, the present invention is directed to a dielectric ceramic composition composed of main component represented by, (100-(a+b+c+d+e+f)} BaTiO 3  +aZnO +bBi 2  O 3+cNb   2  O 5  +dMaO+eMbO 2  +fRe.sub. 2 O 3  (0.5≦a≦4.5, 2.0≦b≦6.0, 0.5≦c≦4.5, 0&lt;d≦4.0, 6.5≦e≦10.0 and 0.5≦f≦5.5) and first by-component. The above-mentioned three dielectric ceramic compositions may also be composed of, 97.0 to 99.94 wt. % of main component, 0.05 to 2.5 wt. % of first by-component, and 0.01 to 0.5 wt. % of second by-component consisting of at least one kind of oxides of Cr, Mn, Fe, Co and Ni.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to dielectric ceramic compositions, and particularly to dielectric ceramic compositions used as materials of a ceramic laminated capacitor and the like.

2. Description of the Prior Art

Conventionally, as dielectric ceramic compositions having a small voltage dependency, a high ceramic strength and a flat dielectric temperature characteristic, those composed of, for example, BaTiO₃ as a main component, to which bismuth compounds such as Bi₂ O₃ -TiO₂ -SnO₂, Bi₂ O₃ -ZrO₂ and rare earth elements are added as by-components, are widely known.

While, separate from the dielectric ceramic compositions having the above-mentioned composition, those composed of BaTiO₃ as a main component, to which Nb₂ O₅, rare earth oxides and transition metal oxides of Cr, Mn, Fe, Co, Ni are added as by-components, have been proposed as the dielectric ceramic composition which has a flat dielectric temperature characteristic, irrespective of its high dielectric constant of 3000 or more.

Temperature characteristics of these dielectric ceramic compositions is that, X7R characteristics of the EIA standards is satisfied, or a capacitive change factor based on an electrostatic capacity at +25° C. in a temperature range of -55° C. to +125° C. is within ±15%.

In recent years, ceramic laminated capacitors are used in ECC modules (electronic control devices of an engine) installed in an engine soon of an automobile. Since the device is designed for stable control of the engine, viewing from the temperature stability of circuitries, it is desirable to satisfy the R characteristics (capacitive change factor within ±15%) as the temperature characteristics of the capacitors being used.

While, in winter in cold districts, temperature goes down to around -20° C. in the engine room of the automobile, and in summer, the temperature rises to around +130° C. when the engine is started. Particularly, when the engine is over heated, the temperature easily goes up to around 150° C. Thus, the conventional dielectric ceramic compositions which satisfy the X7R characteristics can not cope with the high engine room temperature any longer.

Since the laminated capacitors are for use in the automobile, when it breaks, while being mounted on the circuit board, the ECC modules can not function sufficiently, and in the worst case, there is the possibility of causing an accident, which must be avoided by all means. Furthermore, since vibration and stress are always exerted while the automobile is running, in order to avoid damages due to such vibration and stress, the ceramics must be sufficiently strong.

When the voltage dependency of the dielectric ceramic composition is large, the dielectric can not be processed into a thin film, thus the small-sized and large capacity ceramic laminated capacitor can not be manufactured, besides, it is also not preferable from a viewpoint of circuit stability.

Now, in some cases, the dielectric ceramic composition composed of BaTiO₃ as a main component, to which Nb₂ O₅, rare earth compounds and transition metal oxides of Cr, Mn, Fe, Co and Ni are added as by-components, was problematic in that, it is apt to break at the time of mounting to the circuit board because the ceramic strength is weak.

Since the voltage dependency of the dielectric ceramic composition having a large dielectric constant is large, it can not meet with the recent thin-film technique, thus the small-sized and large capacity ceramic laminated capacitor could not be manufactured.

Meanwhile, as stated above, though the dielectric ceramic compositions composed of BaTiO₃ as the main component, to which bismuth compounds are added as the by-components, have a small voltage dependency and a high ceramic strength, when the dielectric constant is raised, a temperature change factor of the dielectric constant becomes larger. Also, in the case of ceramic laminated capacitor, when a baking temperature is raised to 1160° C. of higher , an internal electrode must contain Pb by 30 wt. % or more. Hence, Pb and Bi₂ O₃ in the internal electrode apt to react one another, furthermore, a cost of the internal electrode increases.

SUMMARY OF THE INVENTION

It is, therefore, a primary object of the present invention to provide dielectric ceramic compositions, which can be baked at temperature of 1160° C. or less and satisfies X8R characteristics irrespective of its high dielectric constant of 1000 or more, that is, when based on an electrostatic capacity at +25° C., the temperature change factor (hereinafter, referred to as "TC") of the electrostatic capacity is flat within JL 15% in a wide temperature range of -55° C. to +150° C., and a mechanical strength of the ceramics is high, furthermore, when the thickness of a dielectric ceramic layer is processed into a thin film of 10 μm to 15 μm, and a d.c. voltage of 25V (50% of the rated voltage of 50V) is applied in accordance with the RB characteristics standard of JIS C6429, the temperature change factor of the electrostatic capacity (hereinafter, referred to as "bias TC") is within +15% to 40%.

A first invention is directed to the dielectric ceramic composition composed of, 97.5 to 99.5 wt. % of main component represented by a general formula {100-(a+b+c+d)}(Ba_(100-x) Pbx)TiO₃ +aZnO+bBi₂ O₃ +cNb₂ O₅ +dRe₂ O₃ (where, Re is at least one kind selected from La, Pr, Nd, Sm, Dy and Er, a, b, c, d and x designate mol %, 0.5≦a≦4.5, 0.5≦b≦4.5, 0.5≦c≦4.5, 0.5≦d≦5.5 and 0<x≦6.0) , and 0.05 to 2.5 wt. % of first by-component consisting of glass whose main component is SiO₂.

A second invention is directed to the dielectric ceramic composition composed of, 97.0 to 99.94 wt. % of main component represented by a general formula (100-(a+b+c +d)} (Ba_(100-x) Pb_(x))TiO₃ +aZnO+bBi₂ O₃ +cNb₂ O₅ +dRe₂ O₃ (where, Re is at least one kind selected from La, Pr, Nd, Sm, Dy and Er, a, b, c, d and x designate mol. %, 0.5≦a<4.5, 0.5≦b≦4.5, 0.5≦c≦4.5, 0.5≦d≦5.5 and 0<x≦6.0 ), 0.05 to 2.5 wt. % of first by-component consisting of glass whose main component is SiO₂, and 0.01 to 0.5 wt. % of second by-component consisting of at least one kind selected from oxides of Cr, Mn, Fe, Co and Ni.

A third invention is directed to the dielectric ceramic composition composed of, 97.5 to 99.95 wt. % of main component represented by a general formula (100-(a+b+c+d+e)}BaTiO₃ +aZnO+bBi₂ O₃ +cMeO₂ +dNb₂ O₅ +eRe₂ O₃ (where, Me is at least one kind selected from Ti, Zr and Sn, Re is at least one kind selected from La, Pr, Nd, Sm, Dy and Er, a, b, c, d and e designate mol. %, 0.5≦a≦4.5, 2.0≦b≦6.0, 0.5≦c≦6.5, 0.5≦d≦4.5 and 0.5≦e≦5.5), and 0.05 to 2.5 wt. % of first by-component consisting of glass whose main component is SiO₂.

A fourth invention is directed to the dielectric ceramic composition composed of, 97.0 to 99.94 wt. % of main component represented by a general formula {100-(a+b+c d+e)} BaTiO₃ +aZnO+bBi₂ O₃ +cMeO₂ +dNb₂ O₅ +eRe₂ O₃ (where, Me is at least one kind selected from Ti, Zr and Sn, Re is at least one kind selected from La, Pr, Nd, Sm, Dy and Er, a, b, c, d and e designate mol. %, 0.5≦a≦4.5, 2.0≦b ≦6.0, 0.5≦c≦6.5, 0.5≦d≦4.5and0.5≦e≦5.5),0.05 to 2.5 wt. % of first by-component consisting of glass whose main component is SiO2, and 0.01 to 0.5 wt. % of second by-component consisting of at least one kind from oxides of Cr, Mn, Fe, Co and Ni.

A fifth invention is directed to a dielectric ceramic composition composed of, 97.5 to 99.95 wt. % of main component represented by a general formula (100-(a+b+c+d+e+ f) BaTiO₃ +aZnO+bBi₂ O₃ +cNb₂ O₅ +dMaO+eMbO₂ +fRe₂ O₃ (where, Ma is at least one kind selected from Pb and Ca, Mb is at least one kind selected from Ti, Zr and Sn, Re is at least one kind selected from La, Pr, Nd, Sm, Dy and Er, a, b, c, d, e and f designate mol. %, 0.5≦a≦4.5, 2.0≦b≦6.0, 0.5≦c≦4.5, 0<d≦4.0, 6.5≦e≦10.0 and 0.5≦f ≦5.5), and 0.05 to 2.5 wt. % of first by-component consisting of glass whose main component is SiO₂.

A sixth invention is directed to a dielectric ceramic composition composed of, 97.0 to 99.94 wt. % of main component represented by a general formula (100-(a+b+c+d+e+f) BaTiO₃ +aZnO+bBi₂ O₃ +cNb₂ O₅ +dMaO+eMbO₂ +fRe₂ O₃ (where, Ma is at least one kind selected from Pb and Ca, Mb is at least one kind selected from Ti, Zr and Sn, Re is at least one kind selected from La, Pr, Nd, Sm, Dy and Er, a, b, c, d, e and f designate mol. %, 0.5≦a≦4.5, 2.0≦b≦6.0, 0.5≦c≦4.5, 0<d≦4.0, 6.5≦e≦10.0 and 0.5≦f ≦5.5), and 0.05 to 2.5 wt. % of first by-component consisting of glass whose main component is SiO₂, and 0.01 to 0.5 wt. % of second by-component consisting of at least one kind selected from oxides of Cr, Mn, Fe, Co and Ni.

Hereupon, as the glass which is the by-component consisting of SiO₂ as the main component, there is, for example, BaO--SrO--CaO--Li₂ O--SiO₂. This glass is a sintering assistant which brings the baking temperature to 1160° C. or lower, but it is not limited thereto, oxide glass containing boron such as BaO--Li₂ O--B₂ O₃ --SiO₃ may also be used. The non-oxide glass such as SiO₂ --B₄ C may also be used. The SiO₂ --B₄ C glass is particularly useful when a molding binder of ceramic materials is a water binder.

The dielectric ceramic compositions according to the present invention can be baked at 1160° C. or lower, and in a wide temperature range of -55° C. to +150° C., its TC satisfies the R characteristic and its temperature characteristic is flat. Thus, a ceramic laminated capacitor using these dielectric ceramic compositions can be used in all kinds of electrical equipments which are installed in locations, where the temperature change is large under various conditions.

Since the mechanical strength of the ceramics is high, when used as the ceramic laminated capacitor, destructions such as cracks and, flaws at mounting to the circuit board are eliminated. And hence, accidents caused by improper short-circuit and exoergical damages can be prevented.

Furthermore, since the bias TC is small, the dielectric ceramic layer can be processed into a thin film of 10 μm to 15 μm thick, thus the small-sized and large capacity ceramic laminated capacitor can be realized.

The above and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description made with reference to the drawings.

DESCRIPTION OF THE PREFERRED EMBODIMENTS (Embodiment 1)

First, a method of preparing a main component of a dielectric ceramic composition is described. As starting materials, the industrial materials such as BaTiO₃, PbO, TiO₂, ZnO, Bi₂ O₃, Nb₂ O₅ and Re₂ O₃ (Re is one of La, Pr, Nd, Sm, Dy and Er) were prepared. The starting materials were weighed to have composition ratios as shown in Table 1, then evaporated and dried after mixing and grinding for 16 hours in a wet ball mill to obtain a powdered mixture. The resulting powdered mixture introduced into a zirconia box was calcined at 1000° C. for 2 hour in a natural atmosphere, then roughly ground so as to pass through a sieve of 200 meshes to obtain the material powder for main component of the dielectric ceramic composition.

Next, a method of preparing a first by-component of the dielectric ceramic composition is described. In this embodiment, as the first by-component which brings the baking temperature to 1160° C. or lower, oxide glass whose composition is represented by 8 BaO--6 SrO--6 CaO--30 Li₂ O--50SiO₂ (mol. %) was used. As starting materials, the industrial materials such as BaCO₃, SrCO₃, CaCO₃, Li₂ O and SiO₂ were prepared. The starting materials were weighed to have the above-mentioned composition, then evaporated and dried after mixing and grinding for 16 hours in a wet ball mill to obtain a powdered mixture. The resulting powdered mixture was introduced into a crucible made of alumina and shelved for 1 hour at 1300° C., then quenched for vitrification. The glassy product was ground so as to pass through a sieve of 200 meshes to obtain the material powder for first by-component of the dielectric ceramic composition.

The material powder of first by-component of the dielectric ceramic composition obtained in a manner mentioned above was added to the material powder for main component of the dielectric ceramic composition to obtain weight per-cents as shown in Table 1.

For second by-component, the industrial materials such as Cr₂ O₃, MnO₂, Fe₂ O₃, Co₂ O₃ and NiO were prepared. The second by-component was added to the main component whose composition is 93.0 (Ba₉₇ Pb₃) TiO₃ --1.5 ZnO--1.5 Bi ₂ O₃ 2.0 Nb₂ O₅ --2.0 Nd₂ O₃ (mol. %), to which 1.0 wt. % of the above-mentioned first by-component is added, to obtain composition ratios as shown in Table 2.

To these additives, a polyvinyl butyral binder and an organic solvent such as toluene, ethyl alcohol and the like were added, and mixed in a wet ball mill for 16 hours, then molded into a sheet by a doctor blade method to obtain a green sheet. A thickness of the green sheet was 19 m. After printing an internal electrode pattern on the green sheet with a paste of Ag/Pd=70/30 (wt. %), 6 layers of green sheets are laminated and pressed together with dummy sheets to obtain a laminate. Molded pieces of 5.5 mm length ×4.5 mm width ×1 mm thickness were cut out from the laminate. Thereafter, the molded pieces were baked at baking temperatures shown in Table 3 and Table 4 for 2 hours to obtain a sinter. A thickness of the sintered dielectric was 13 μm.

Then, a silver electrode was baked onto an end face of the resulting sinter to obtain a subject (a laminated capacitor), whose dielectric constant (ε), dielectric loss (tan δ), TC and bias TC were measured.

In this case, the dielectric constant (ε) and dielectric loss (tan δ) were measured at the condition of 25° C., 1 KHz and 1 Vrms. As the TC, a maximum value of temperature change factor, or a maximum change factor (ΔC max), between -55° C. and +150° C. was obtained, based on an electrostatic capacity at 25° C. For the bias TC, as same as the TC, a maximum change factor (ΔC_(maxB)) was obtained, based on an electrostatic capacity at 25° C. and applied voltage of 0° C., by measuring the electrostatic capacity as superposing the d.c. voltage 25V on the subject within the above-mentioned temperature range.

A deflective strength of the ceramic was measured by a 3-point bending method. The material sheets having the composition shown in Table 1 and Table 2 were pressed and molded to obtain a laminate, and mold pieces of 35 mm length ×7 mm width ×1.2 mm thickness were cut out from the laminate. Thereafter, the mold pieces were baked at the baking temperatures shown in Table 3 and Table 4 for 2 hours to obtain rectangular-shape ceramics. In such a manner, the deflective strength was measured on 20 samples for respective compositions to obtain the mean deflective strength of the ceramics of respective compositions.

Experiment results of the compositions in Table 1 as shown in Tale 3, and those of the compositions in Table 2 are shown in Table 4.

The reason for restricting ranges of the main component quantity, first by-component quantity and second by-component quantity in the present invention, is described.

First, the reason for restricting the main component composition is described.

The reason why a value of a or ZnO is 0.5 to 4.5 mol. % is that, as Sample No. 9, if it is below 0.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)), and also the defective strength becomes 1500 kg/cm² or less. Also, as Sample No. 10, if it exceeds 4.5 mol. %, the TC exceeds - 15% at the maximum change factor (ΔC_(max)) and also the bias TC exceeds -40%.

The reason why a value of b or Bi₂ O₃ is 0.5 to 4.5 mol. % is that, as Sample No. 11, if it is below 0.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)) and also the deflective strength becomes 1500 Kg/cm² or less. Also, as Sample No. 12, if it exceeds 4.5 mol. %, a dielectric constant (ε) becomes less than 1000.

The reason why a value of c or Nb₂ 0₅ is 0.5 to 4.5 mol. % is that, as Sample No. 13, if it is below 0.5 mol. %, or as Sample No. 14, if it exceeds 4.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)) and also the bias TC exceeds -40%.

The reason why a value d or Re₂ O₃ is 0.5 to 5.5 mol. % is that, as Sample No. 15, if it is below 0.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)) and also the bias TC exceeds -40%. Also, as Sample No. 16, if it exceeds 5.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)).

As to a value of x or PbTiO₃, as Sample No. 17, if it exceeds 6.0 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)) and also the bias TC exceeds -40%.

Next, the reason for restricting the first by-component quantity is described.

The reason why the first by-component quantity is 0.05 to 2.5 wt. % is that, as Sample No. 18, if it is below 0.05 wt. %, the baking temperature exceeds 1160° C. Also, as Sample No. 21, if it exceeds 2.5 wt. %, the dielectric constant (ε) becomes less than 1000.

Next, the reason for restricting the second by-component quantity is described.

The second by-component is for preventing reduction of the dielectric ceramic, and the reason why its quantity is restricted to 0.01 to 0.5 wt. % is that, if it is below 0.01 wt. %, the reduction preventing effect is spoiled, and as Sample No. 31, if it exceeds 0.5 wt. %, a dielectric loss (tan δ) exceeds 2.5%.

(Embodiment 2)

First, a method of preparing a main component of a dielectric ceramic composition is described. As starting materials, the industrial materials such as BaTiO₃, ZnO, Bi₂ O₃, MeO₂ (Me is one of Ti, Zr and Sn), Nb₂ O₅, Re₂ O₃ (Re is one of La, Pr, Nd, Sm, Dy and Er) were prepared. The starting materials were weighed to have composition ratios as shown in Table 5, then evaporated and dried after mixing and grinding for 16 hours in a wet ball mill to obtain a powdered mixture. The resulting powdered mixture introduced into a zirconia box was calcined at 1000° C. for 2 hours in a natural atmosphere, then roughly ground so as to pass through a sieve of 200 meshes to obtain the material powder for main component of the dielectric ceramic composition.

Next, a method of preparing a first by-component of the dielectric ceramic composition is described. In this embodiment, as the first by-component which brings the baking temperature to 1160° C. or lower, oxide glass whose composition is represented by 8 BaO--6 SrO--6 CaO--30 Li₂ O--50 SiO₂ (mol. %) was used. As starting materials, the industrial materials such as BaCO₃, SrCO₃, CaCO₃, Li₂ O and SiO₂ were prepared. The starting materials were weighed to have the above-mentioned composition, then evaporated and dried after mixing and grinding for 16 hours in a wet ball mill to obtain a powdered mixture. The resulting powdered mixture was introduced into a crucible made of alumina and shelved for 1 hour at 1300° C., then quenched for vitrification. The glassy product was ground so as to pass through a sieve of 200 meshes to obtain the material powder for first by-component of the ceramic composition.

The material powder for first by-component of the dielectric ceramic composition obtained in a manner mentioned above was added to the material powder for main component of the dielectric ceramic composition to obtain weight per-cents as shown in Table 5.

For second by-component, the industrial materials such as Cr₂ O₃, MnO₂, Fe₂ O₃, Co₂ O₃ and NiO were prepared. The second by-component was added to the main component, whose composition is 90.5 BaTiO₃ --1.5 ZnO--3.0 Bi₂ O₃ --1.0 TiO₂ --0.5 ZrO₂ --1.5 Nb₂ O₅ --1.5 Nd₂ O₃ --0.5 Dy₂ O₃ (mol. %) to which 1.0 wt. % of the above-mentioned first by-component is added, to obtain composition ratios as shown in Table 6.

To these additives, a polyvinyl butyral binder and an organic solvent such as toluene, ethyl alcohol and the like were added and mixed in a wet ball mill for 16 hours, then molded into a sheet by a doctor blade method to obtain a green sheet. A thickness of the green sheet was 19 μm. After printing an internal electrode pattern on the green sheet with a paste of Ag/Pd=70/30 (wt. %), 6 layers of green sheets were laminated and pressed together with dummy sheets to obtain a laminate. Mold pieces of 5.5 mm length ×4.5 mm width ×1 mm thickness were cut out from the laminate. Thereafter, the molds pieces were baked at baking temperatures shown in Table 7 and Table 8 for 2 hours to obtain a sinter. A thickness of the sintered dielectric was 13 μm.

Then, a silver electrode was baked onto an end face of the resulting sinter to obtain a subject (a laminated capacitor), whose dielectric constant (ε), dielectric loss (tan δ), TC and bias TC were measured.

In this case, the dielectric constant (ε) and dielectric loss (tan δ) were measured at the condition of 25° C., 1 KHz and 1 Vrms. As the TC, a maximum value of temperature change factor, or a maximum change factor (ΔC_(max)), between -55° C. and +150° C. was obtained, based on an electrostatic capacity at 25° C. For the bias TC, as same as the TC, a maximum change factor (ΔC_(maxB)) was obtained, based on an electrostatic capacity at 25° C. and applied voltage of 0V, by measuring the electrostatic capacity as superposing the d.c. voltage of 25V on the subject within the above-mentioned temperature range.

A deflective strength of the ceramic was measured by a 3-point bending method. First, the material sheets having the compositions shown in Table 5 and Table 6 were pressed and molded to obtain a laminate, and mold pieces of 35 mm length ×7 mm width ×1.2 mm thickness were cut out from the laminate. Thereafter, the mold pieces were baked at the baking temperature shown in Table 7 and Table 8 for 2 hours to obtain rectangular-shape ceramics. In such a manner, the deflective strength was measured on 20 samples for respective compositions to obtain the mean deflection strength of the ceramics of respective compositions.

Experiment results of the compositions in Table 5 are shown in Table 7, and those of the compositions in Table 6 are shown in Table 8.

The reason for restricting ranges of the main component quantity, first by-component quantity and second by-component quantity in the present invention, is described.

First, the reason for restricting the main component composition is described.

The reason why a value of a or ZnO is 0.5 to 4.5 mol. % is that, as Sample No. 109, if it is below 0.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)) and also the deflective strength becomes 1500 kg/cm² or less. Also, as Sample No. 110, if it exceeds 4.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)) and also the bias TC exceeds -40%.

The reason why a value of b or Bi₂ O₃ is 2.0 to 6.0 mol. % is that, as Sample No. 111, if it is below 2.0 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)), and also the deflective strength becomes 1500 kg/cm² or less. also, as Sample No. 112, if it exceeds 6.0 mol. %, the dielectric constant (ε) becomes less than 1000.

The reason why a value of c or MeO₂ is 0.5 to 6.5 mol. % is that, as Sample No. 113, if it is below 0.5 mol. % or as Sample No. 114, if it exceeds 6.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)).

The reason why a value of d or Nb₂ O₅ is 0.5 to 4.5 mol. % is that, as Sample NO. 115, if it is below 0.5 mol. % or also as Sample No. 116, if it exceeds 4.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)) and also the bias TC exceeds -40%.

The reason why a value of e or Re₂ O₃ is 0.5 to 5.5 mol. % is that, as Sample No. 117, if it is below 0.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)), and also the bias TC exceeds -40%. Also, as Sample No. 118, if it exceeds 5.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)).

Next, the reason for restricting the first by-component quantity is described.

The reason why the first by-component quantity is restricted to 0.05 to 2.5 wt. % is that, as Sample No. 119 shown in Table 5, if it is below 0.05 wt. %, the baking temperature exceeds 1160° C. While, as Sample No. 122, if it exceeds 2.5 wt. %, the dielectric constant (ε) becomes less than 1000.

Next, the reason for restricting the second by-component quantity is described.

The second by-component is for preventing reduction of the dielectric ceramics, and the reason why its range is restricted to 0.01 to 0.5 wt. % is that, if it is below 0.01 wt. %, the reduction preventing effect is spoiled, and as Sample No. 132 shown in Table 6, if it exceeds 0.5 wt. %, the dielectric loss (tan δ) exceeds 2.5%.

(Embodiment 3 )

First, a method of preparing a main component of a dielectric ceramic composition is described. As starting materials, the industrial materials such as BaTiO₃, ZnO, Bi₂ O₃, Nb₂ O₅, MaO (Ma is one of Pb and Ca), MeO₂ (Me is one of Ti, Zr and Sn), Re₂ O₃ (Re is one of La, Pr, Nd, Sm, Dy and Er) were prepared. The starting materials were weighed to have composition ratios as shown in Table 9, then evaporated and dried after mixing and grinding for 16 hours in a wet ball mill to obtain a powdered mixture. The resulting powdered mixture introduced into a zirconia box was calcined at 1000° C. for 2 hours in a natural atmosphere, then roughly ground so as to pass through a sieve of 200 meshes to obtain the material powder for main component of the dielectric ceramic composition.

Next, a method of preparing a first by-component of the dielectric ceramic composition is described. In this embodiment, as the first by-component which brings the baking temperature to 1160° C. or lower, oxide glass whose main component is represented by 8 BaO--6 SrO--6 CaO--30 Li₂ O -50SiO₂ (mol. %) was used. As starting materials, the industrial materials such as BaCO₃, SrCO₃, CaCO₃, Li₂ O and SiO₂ were prepared. These starting materials were weighed to have the above-mentioned composition, then evaporated and dried after mixing and grinding in a wet ball mill for 16 hours to obtain a powdered mixture. The resulting powdered mixture was introduced into a crucible made of alumina and shelved for 1 hour at 1300° C., then quenched for vitrification. The glassy product was ground so as to pass through a sieve of 200 meshes to obtain the material powder for first by-component of the ceramic composition.

The material powder for first by-component of the dielectric ceramic competition obtained in a manner mentioned above was added to the material powder for main component of the dielectric ceramic compositions to obtain weight per-cents as shown in Table 9.

For second by-component, the industrial materials such Cr₂ O₃, MnO₂, Fe₂ O₃, Co₂ O₃ and NiO were prepared. The second by-component was added to the main component-whose composition is 88.5 BatiO₃ --1.5 ZnO--3.0 Bi₂ O₃ --1.0 Nb₂ O₅ --2.0 PbO--1.0 TiO₂ --0.5 SnO₂₋₋₀.5 ZrO₂ --2.0 Nd₂ O₃ (mol. %), to which 1.0 wt. % of the above-mentioned first by-component is added, to obtain the composition ratios as shown in Table 10.

To these additives, a polyvinyl bytyral binder and an organic solvent such as toluene, ethyl alcohol and the like were added and mixed in a wet ball mill for 16 hours, then molded into a sheet by a doctor blade method to obtain a green sheet. A thickness of the green sheet was 19 μm. After printing an internal electrode pattern on the green sheet with a paste of Ag/Pd=70/30 (wt. %), 6 layers of green sheets were laminated and pressed together with dummy sheets to obtain a laminate, and mold pieces of 5.5 mm length ×4.5 mm width ×1 mm thickness were cut out from the laminate. Thereafter, the mold pieces were baked at the baking temperatures shown in Table 11 and Table 12 for 2 hours to obtain a sinter. A thickness of the sintered dielectric was 13 μm.

Then, a silver electrode was baked onto an end face of the resulting sinter to obtain a subject (a laminated capacitor), whose dielectric constant (ε), dielectric loss (tan δ), TC and bias TC were measured.

In this case, the dielectric constant (ε) and dielectric loss (tan δ) were measured at the condition of 25° C., 1 KHz and 1Vrms. As the TC, a maximum value of temperature change factor, or a maximum change factor (ΔC_(max)), between -55° C. and +150° C. was obtained, based on an electrostatic capacity at 25° C. For the bias TC, as same as the TC, a maximum change factor (ΔC_(maxB)) was obtained, based on an electrostatic capacity at 25° C. and applied voltage of 0V, by measuring the electrostatic capacity as superposing the d.c. voltage of 25V on the subject within the above-mentioned temperature range.

A deflective strength of the ceramic was measured by a 3-point bending method. First, the material sheets having the compositions shown in Table 9 and Table 10 were pressed and molded to obtain a laminate, from which mold pieces of 35 mm length ×7 mm width ×1.2 mm thickness were cut out. Thereafter, the mold pieces were baked at the baking temperatures shown in Table 11 and Table 12 for 2 hours to obtain rectangular-shape ceramics. In such a manner, the deflective strength was measured on 20 samples for respective compositions to obtain the mean deflective strength of the ceramics of the respective compositions.

Experiment results of the compositions in Table 9 are shown in Table 11, land those of the compositions in Table 10 are shown in Table 12.

The reason for restricting ranges of the main component quantity, first by-component quantity and second by-component quantity in the present invention is described.

First, the reason for restricting the main component composition is described.

The reason why a value of a or ZnO is 0.5 to 4.5 mol. % is that, as Sample No. 209, if it is below 0.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)), and also the deflective strength becomes 1500 kg/cm² or less. Also, as Sample No. 210, if it exceeds 4.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)) and also the bias TC exceeds -40%.

The reason why a value of b or Bi₂ O₃ is 2.0 to 6.0 mol. % is that, as Sample No. 211, if it is below 2.0 wt. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)), and also the deflective strength becomes 1500kg/cm² or less. Also, as Sample No. 212, if it exceeds 6.0 mol. %, the dielectric constant (ε) becomes less than 1000.

The reason why a value of C or Nb₂ O₃ is 0.5 to 4.5 mol. % is that, as Sample No. 213, if it is below 0.5 mol. % or as Sample No. 214, if it exceeds 4.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)) and also the bias TC exceeds -40%.

The reason why a value of d or MaO is 4.0 mol. % or less is that, as Sample No. 215, if it exceeds 4.0 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)).

The reason why a value of e or MbO₂ is 6.5 to 10.0 mol. % is that, as Sample No. 216, if it is below 6.5 mol. % or as Sample No. 217, if it exceeds 10.0 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)).

The reason why a value of f or Re₂ O₃ is 0.5 to 5.5 mol. % is that, as Sample No. 218, if it is below 0.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)) and also the bias TC exceeds -40%. Also, as Sample No. 219, if it exceeds 5.5 mol. %, the TC exceeds -15% at the maximum change factor (ΔC_(max)).

Next, the reason for restricting the first by-component quantity is described.

The reason why the first by-component quantity is 0.05 to 2.5 wt. % is that, as Sample No. 220 shown in Table 9, if it is below 0.05 wt. %, the baking temperature exceeds 1160° C. While, as Sample No. 222, if it is exceeds 2.5 wt. %, the dielectric constant (ε) becomes less than 1000.

Next, the reason for restricting the second by-component quantity is described.

The second by-component is for preventing reduction of the dielectric ceramics, and the reason why the second by-component quantity is restricted to 0.01 to 0.5 wt. % is that, if it is below 0.01 wt. %, the reduction preventing effect is spoiled, and as Sample No. 232 shown in Table 10, if it exceeds 0.5 wt. %, the dielectric loss (tan δ) exceeds 2.5%.

In the above-mentioned embodiments, the by-components, which are prepared into a predetermined composition ratio beforehand, and ground for vitrification after heating and melting at high temperature, were added to and blended with the main components of the ceramic compositions.

However, as a method of adding the first by-component, alternatively, the starting materials, which are modified by preparing into a predetermined ratio beforehand and heating to temperature just before the melting point may be added, or composition elements of the first by-component may be individually added to the main component at any state such as metal alkoxide so as to melt and react during baking for vitrification.

In the above-mentioned embodiments, also in the case of second by-component, though it is added in the form of oxides from the beginning, as the starting materials at the time of preparing the materials, carbonates of the elements which turn into oxides during calcining and baking may also be used.

While the present invention has been particularly described, it is to be understood that such description is used merely as an example rather than limitation, and the spirit and scope of the present invention is determined solely by the terms of the appended claims.

                                      TABLE 1                                      __________________________________________________________________________     main component compositon (mol %)                                              {100 - (a + b + c + d)} (Ba.sub.100-x Pb.sub.x)TiO.sub.3 + aZnO +              bBi.sub.2 O.sub.3 + cNb.sub.2 O.sub.5 + dRe.sub.2 O.sub.3                                                                         main  first by-             Sample                 d                           component                                                                            component             No. 100 - (a + b + c + d)                                                                       a b c La.sub.2 O.sub.3                                                                   Pr.sub.2 O.sub.3                                                                   Nd.sub.2 O.sub.3                                                                    Sm.sub.2 O.sub.3                                                                   Dy.sub.2 O.sub.3                                                                   Er.sub.2 O.sub.3                                                                   x  (wt %)                                                                               (wt                   __________________________________________________________________________                                                              %)                     1  93           1.5                                                                              2.5                                                                              2 0   0   1    0   0   0   1  99    1                      2  89           2 4 3 0.5 1   0    0   0.5 0   1.5                                                                               98    2                      3  87.5         1 4.5                                                                              4 0   0   2.5  0   0.5 0   1  99.5  0.5                    4  91           4 2 1 0.5 0   0    0.5 0   1   5  99    1                      5  93           1.5                                                                              3 1.5                                                                              0   0.5 0    0   0   0.5 4  98.5  1.5                    6  86.5         2.5                                                                              3 3 2.5 0   2.5  0   0   0   2  99.5  0.5                    7  88.5         4.5                                                                              2.5                                                                              2 0   1   0    0   1.5 0   3  98    2                      8  86.5         1.5                                                                              3 4.5                                                                              0   0   2.5  1.5 0   0.5 1.5                                                                               98    2                      *9 93.7         0.3                                                                              2.5                                                                              2 0.5 0   0.5  0   0.5 0   2  99    1                     *10 86.8         4.7                                                                              4 3 0   0   1.5  0   0   0   1.5                                                                               99.5  0.5                   *11 93.2         1.5                                                                              0.3                                                                              2.5                                                                              0   0   0    2   0   0.5 0.5                                                                               98    2                     *12 85.8         2 4.7                                                                              4.5                                                                              0   0   3    0   0   0   1.0                                                                               99.5  0.5                   *13 92.7         1 4 0.3                                                                              0   2   0    0   0   0   1.0                                                                               99    1                     *14 88.8         1.5                                                                              2.5                                                                              4.7                                                                              0   0   0    2.5 0   0   1.5                                                                               99    1                     *15 93.7         1.5                                                                              2.5                                                                              2 0.3 0   0    0   0   0   2  99    1                     *16 87.8         1.5                                                                              3 2 0   0.7 2.5  2.5 0   0   2.5                                                                               99.5  0.5                   *17 87.5         1 4.5                                                                              4 0   0   2.5  0   0.5 0   6.2                                                                               99.5  0.5                   *18 93           1.5                                                                              2.5                                                                              2 0   0   1    0   0   0   1.0                                                                               100   0                      19 91.5         4 2 1 0   0   1.5  0   0   0   1.0                                                                               99.95 0.05                   20 92           1.5                                                                              2.5                                                                              2 0   0   2    0   0   0   2.5                                                                               97.5  2.5                   *21 91           4 2 1 0   0   2    0   0   0   0.5                                                                               97.3  2.7                   __________________________________________________________________________      *indicates out of the scope of the invention                             

                  TABLE 2                                                          ______________________________________                                               main      first by-                                                      Sample                                                                               component component second by-component (wt %)                           No.   (wt %)    (wt %)    Cr   Mn   Fe   Co   Ni                               ______________________________________                                         22    98.99     1.0       0    0.01 0    0    0                                23    98.85     1.0       0.05 0.05 0.05 0    0                                24    98.95     1.0       0    0    0    0.05 0                                25    98.9      1.0       0.05 0    0    0    0.05                             26    98.85     1.0       0    0.1  0    0    0.05                             27    98.65     1.0       0.05 0.2  0.05 0.05 0                                28    98.6      1.0       0    0.3  0    0    0.1                              29    98.55     1.0       0    0.3  0    0.1  0.05                             30    98.5      1.0       0.1  0.3  0    0.1  0                                *31   98.45     1.0       0    0.35 0.05 0.1  0.05                             ______________________________________                                          *indicates out of the scope of the invention                             

                                      TABLE 3                                      __________________________________________________________________________     baking     electronic property mechanical property                             Sample                                                                             temperature    TC (%)                                                                              bias TC (%)                                                                           deflective strength                             No. (°C.)                                                                          ε                                                                         tan δ (%)                                                                     ΔC.sub.max                                                                    ΔC.sub.maxB                                                                     (kg/cm.sup.2)                                   __________________________________________________________________________      1  1140   2020                                                                              1.6  -12.8                                                                               -33.0  2070                                             2  1100   1810                                                                              1.5  -13.9                                                                               -30.0  2400                                             3  1100   1690                                                                              1.6  -14.0                                                                               -30.3  2180                                             4  1160   2020                                                                              1.7  10.0 -34.0  1910                                             5  1120   1770                                                                              1.7  11.0 -31.0  2210                                             6  1080   1360                                                                              1.8  -14.0                                                                               -28.5  2310                                             7  1100   1690                                                                              1.5  10.2 -33.2  2100                                             8  1140   1630                                                                              1.6  11.8 -31.5  2130                                             *9 1160   1680                                                                              2.2  -17.5                                                                               -33.5  1450                                            *10 1080   2130                                                                              1.5  -22.0                                                                               -41.5  2060                                            *11 1080   1620                                                                              1.7  -23.0                                                                               -36.0  1480                                            *12 1080    980                                                                              1.8  -14.5                                                                               -26.5  2310                                            *13 1080   1790                                                                              1.9  -22.5                                                                               -41.0  2270                                            *14 1100   1420                                                                              1.9  -16.0                                                                               -40.8  2010                                            *15 1140   1450                                                                              1.7  -21.0                                                                               -41.1  1970                                            *16 1120   1500                                                                              1.1  -18.2                                                                               -35.1  1820                                            *17 1080   1910                                                                              2.3  18.0 -42.0  2220                                            *18 1160° C. (not sintered)                                              19 1160   1680                                                                              2.0  13.0 -36.0  1870                                             20 1080   1290                                                                              1.9  14.0 -33.5  2130                                            *21 1080    930                                                                              2.1  14.1 -34.5  2100                                            __________________________________________________________________________      *indicates out of the scope of the invention                             

                                      TABLE 4                                      __________________________________________________________________________     baking     electronic property mechanical property                             Sample                                                                             temperature    TC (%)                                                                              bias TC (%)                                                                           deflective strength                             No. (°C.)                                                                          ε                                                                         tan δ (%)                                                                     ΔC.sub.max                                                                    ΔC.sub.maxB                                                                     (kg/cm.sup.2)                                   __________________________________________________________________________     22  1100   2000                                                                              1.7  -11.8                                                                               -31.0  2060                                            23  1100   1910                                                                              1.7  -12.0                                                                               -31.5  2010                                            24  1100   1970                                                                              1.8  -11.8                                                                               -31.0  1970                                            25  1100   1940                                                                              1.8  -11.5                                                                               -30.8  2070                                            26  1100   1970                                                                              1.5  -11.5                                                                               -31.0  2060                                            27  1100   1850                                                                              2.1  -12.0                                                                               -31.7  1970                                            28  1100   1900                                                                              2.1  -11.5                                                                               -31.1  1950                                            29  1100   1960                                                                              2.2  -11.8                                                                               -32.0  1960                                            30  1100   1920                                                                              2.3  -11.6                                                                               -31.3  1970                                            *31 1100   1920                                                                              2.8  -11.4                                                                               -31.1  2010                                            __________________________________________________________________________      *indicates out of the scope of the invention                             

                                      TABLE 5                                      __________________________________________________________________________     main component composition (mol %)                                             {100 - (a + b + c + d + e)} BaTiO.sub.3 + aZnO + bBi.sub.2 O.sub.3 +           cMeO.sub.2 + dNb.sub.2 O.sub.5 + eRe.sub.2 O.sub.3                             100 - (a +                                         main  first by-             Sample                                                                             b + c +    c           e                       component                                                                            component             No. d + e) a b TiO.sub.2                                                                         ZrO.sub.2                                                                          SnO.sub.2                                                                         d La.sub.2 O.sub.3                                                                   Pr.sub.2 O.sub.3                                                                   Nd.sub.2 O.sub.3                                                                   Sm.sub.2 O.sub.3                                                                   Dy.sub.2 O.sub.3                                                                   Er.sub.2 O.sub.3                                                                   (wt %)                                                                               (wt                   __________________________________________________________________________                                                              %)                     101                                                                               92     1.5                                                                              2.5                                                                              2  0   0  1 0   0   1   0   0   0   99    1                      102                                                                               89     1 4 1.5                                                                               1.5 0  1.5                                                                              0.5 1   0   0   0   0   98    2                      103                                                                               84     0.5                                                                              5.5                                                                              1.5                                                                               2   1.5                                                                               2 0   0   2.5 0   0.5 0   99.5  0.5                    104                                                                               87     4 2 0.5                                                                               0   0.5                                                                               4 0.5 0   0   0.5 0   1   99    1                      105                                                                               90     1.5                                                                              3 0  0   0.5                                                                               4.5                                                                              0   0.5 0   0   0   0   98.5  1.5                    106                                                                               79.5   2.5                                                                              6 0  5.5 1  0.5                                                                              2.5 0   2.5 0   0   0   99.5  0.5                    107                                                                               87     4.5                                                                              2.5                                                                              2  0   0  1.5                                                                              0   1   0   0   1.5 0   98    2                      108                                                                               86     1.5                                                                              3 0.5                                                                               1.5 0  2 0   0   2.5 1.5 0   1.5 98    2                     *109                                                                               92.7   0.3                                                                              2.5                                                                              0  0.5 1.5                                                                               1 0.5 0   0.5 0   0.5 0   99    1                     *110                                                                               86.3   4.7                                                                              4 0  0.5 0  3 0   0   1.5 0   0   0   99.5  0.5                   *111                                                                               90.2   1.5                                                                              1.8                                                                              1.5                                                                               0.5 0.5                                                                               1.5                                                                              0   0   0   2   0   0.5 98    2                     *112                                                                               81.3   2 6.2                                                                              2  2   2  1.5                                                                              0   0   3   0   0   0   99.5  0.5                   *113                                                                               88.7   2 4 0.3                                                                               0   0  3 0   2   0   0   0   0   99    1                     *114                                                                               84.3   1.5                                                                              5 3  2   1.7                                                                               2.5                                                                              0   0   0   2.5 0   0   99    1                     *115                                                                               91.2   2 2.5                                                                              0.5                                                                               0.5 1  0.3                                                                              0   0   0   0   2   0   99    1                     *116                                                                               82.8   2.5                                                                              4.5                                                                              1  2   1  4.7                                                                              0   0   0   0   0   1.5 99.5  0.5                   *117                                                                               92.7   1.5                                                                              2.5                                                                              0.5                                                                               1.5 0  1 0.3 0   0   0   0   0   99    1                     *118                                                                               85.8   1.5                                                                              3 0.5                                                                               0.5 1  2 0   0.7 2.5 2.5 0   0   99.5  0.5                   *119                                                                               92     1.5                                                                              2.5                                                                              0  0   2  1 0   0   1   0   0   0   100   0                      120                                                                               87.5   4 2 0.5                                                                               0.5 0  4 0   0   1.5 0   0   0   99.95 0.05                   121                                                                               91     1.5                                                                              2.5                                                                              1  0   1  1 0   0   2   0   0   0   97.5  2.5                   *122                                                                               87     4 2 0  0.5 0.5                                                                               4 0   0   2   0   0   0   97.3  2.7                   __________________________________________________________________________      *indicates out of the scope of the invention                             

                  TABLE 6                                                          ______________________________________                                               main      first by-                                                      Sample                                                                               component component second by-component (wt %)                           No.   (wt %)    (wt %)    Cr   Mn   Fe   Co   Ni                               ______________________________________                                         123   98.99     1.0       0    0.01 0    0    0                                124   98.85     1.0       0.05 0.05 0.05 0    0                                125   98.95     1.0       0    0    0    0.05 0                                126   98.9      1.0       0.05 0    0    0    0.05                             127   98.85     1.0       0    0.1  0    0    0.05                             128   98.65     1.0       0.05 0.2  0.05 0.05 0                                129   98.6      1.0       0    0.3  0    0    0.1                              130   98.55     1.0       0    0.3  0    0.1  0.05                             131   98.5      1.0       0.1  0.3  0    0.1  0                                *132  98.45     1.0       0    0.35 0.05 0.1  0.05                             ______________________________________                                          *indicates out of the scope of the invention                             

                                      TABLE 7                                      __________________________________________________________________________     baking     electronic property mechanical property                             Sample                                                                             temperature    TC (%)                                                                              bias TC (%)                                                                           deflective strength                             No. (°C.)                                                                          ε                                                                         tan δ (%)                                                                     ΔC.sub.max                                                                    ΔC.sub.maxB                                                                     (kg/cm.sup.2)                                   __________________________________________________________________________      101                                                                               1140   2010                                                                              1.5  -12.1                                                                               -33.5  2060                                             120                                                                               1100   1790                                                                              1.5  -13.3                                                                               -30.0  2290                                             103                                                                               1100   1800                                                                              1.6  -14.2                                                                               -30.5  2170                                             104                                                                               1160   2010                                                                              1.7  -11.8                                                                               -32.0  1770                                             105                                                                               1120   1760                                                                              1.7  -10.6                                                                               -33.0  2210                                             106                                                                               1080   1370                                                                              1.2  -14.2                                                                               -28.5  2200                                             107                                                                               1100   1620                                                                              1.2  -14.5                                                                               -33.0  2080                                             108                                                                               1100   1640                                                                              1.6  12.1 -31.5  2150                                            *109                                                                               1160   1690                                                                              2.1  -17.5                                                                               -33.8  1480                                            *110                                                                               1120   2220                                                                              1.3  -21.4                                                                               -43.5  2020                                            *111                                                                               1120   1740                                                                              1.8  -23.3                                                                               -37.0  1470                                            *112                                                                               1100    980                                                                              1.3  -14.7                                                                               -28.0  2260                                            *113                                                                               1100   1820                                                                              1.6  -23.5                                                                               -31.0  2300                                            *114                                                                               1140   1510                                                                              1.0  -17.0                                                                               -31.5  2010                                            *115                                                                               1140   1940                                                                              1.1  -22.5                                                                               -41.7  1980                                            *116                                                                               1120   1620                                                                              1.7  -18.0                                                                               -44.8  2100                                            *117                                                                               1160   1540                                                                              1.9  -29.5                                                                               -43.0  2050                                            *118                                                                               1160   1910                                                                              1.2  -24.5                                                                               -35.2  1810                                            *119                                                                               1160° C. (not sintered)                                              120                                                                               1160   1700                                                                              1.3  13.0 -35.0  1620                                             121                                                                               1080   1390                                                                              1.2  13.5 -33.4  2150                                            *122                                                                               1080    950                                                                              1.1  14.1 -34.4  2120                                            __________________________________________________________________________      *indicates out of the scope of the invention                             

                                      TABLE 8                                      __________________________________________________________________________     baking     electronic property mechanical property                             Sample                                                                             temperature    TC (%)                                                                              bias TC (%)                                                                           deflective strength                             No. (°C.)                                                                          ε                                                                         tan δ (%)                                                                     ΔC.sub.max                                                                    ΔC.sub.maxB                                                                     (kg/cm.sup.2)                                   __________________________________________________________________________     123 1120   2000                                                                              1.5  -12.1                                                                               -33.0  2040                                            124 1120   1920                                                                              1.7  -12.0                                                                               -33.3  2020                                            125 1120   2010                                                                              1.5  -12.5                                                                               -34.2  1980                                            126 1120   1970                                                                              1.6  -12.5                                                                               -33.0  2060                                            127 1120   2060                                                                              1.6  -13.0                                                                               -34.0  2050                                            128 1120   1890                                                                              2.0  -12.1                                                                               -33.0  1970                                            129 1120   1920                                                                              2.1  -12.0                                                                               -32.8  1960                                            130 1120   1950                                                                              2.1  -12.5                                                                               -35.5  1970                                            131 1120   1920                                                                              2.2  -12.7                                                                               -33.5  1980                                            *132                                                                               1120   1820                                                                              2.8  -11.8                                                                               -32.2  1990                                            __________________________________________________________________________      *indicates out of the scope of the inveniton                             

                                      TABLE 9                                      __________________________________________________________________________     main component composition (mol %)                                             {100 - (a + b + c + d + e + f)} BaTiO.sub.3 + aZnO + bBi.sub.2 O.sub.3 +       cNb.sub.2 O.sub.5 + dMaO + eMbO.sub.2 + fRe.sub.2 O.sub.3  first                                                                          first                  100 -                                               main                                                                               by-                 Sam-                                                                              (a + b +                                            compo-                                                                             compo-              ple                                                                               c + d +     d     e         f                       nent                                                                               nent                No.                                                                               e + f)                                                                               a b c PbO                                                                               CaO                                                                               TiO.sub.2                                                                         ZrO.sub.2                                                                          SnO.sub.2                                                                         La.sub.2 O.sub.3                                                                   Pr.sub.2 O.sub.3                                                                   Nd.sub.2 O.sub.3                                                                   Sm.sub.2 O.sub.3                                                                   Dy.sub.2 O.sub.3                                                                   Er.sub.2 O.sub.3                                                                   (wt                                                                                (wt                 __________________________________________________________________________                                                                %)                   201                                                                              85.5  1.5                                                                               2.5                                                                             1 0.5                                                                               0  4  2   2  0   0   1   0   0   0   99  1                    202                                                                              82.5  1 4 1.5                                                                              0  0.5                                                                               5  3   1  0.5 1   0   0   0   0   98  2                    203                                                                              80.5  0.5                                                                              5.5                                                                              2 2  0  2  4   0.5                                                                               0   0   2.5 0   0.5 0   99.5                                                                               0.5                  204                                                                              78.5  4 2 4 0  1.5                                                                               4  0   4  0.5 0   0   0.5 0   1   99  1                    205                                                                              78.5  1.5                                                                              3 4.5                                                                              2  2  4  4   0  0   0.5 0   0   0   0   98.5                                                                               1.5                  206                                                                              75    2.5                                                                              6 0.5                                                                              4  0  0  4   3  2.5 0   2.5 0   0   0   99.5                                                                               0.5                  207                                                                              79    4.5                                                                              2.5                                                                              1.5                                                                              0  3  4  2   1  0   1   0   0   1.5 0   98  2                    208                                                                              77.5  1.5                                                                              3 2 1.5                                                                               2  3  2   2  0   0   2.5 1.5 0   1.5 98  2                   *209                                                                              85.2  0.3                                                                              2.5                                                                              1 2  0  4.5                                                                               1   2  0.5 0   0.5 0   0.5 0   99  1                   *210                                                                              77.8  4.7                                                                              4 3 2  0  5  1.5 0.5                                                                               0   0   1.5 0   0   0   99.5                                                                               0.5                 *211                                                                              84.2  1.5                                                                              1.8                                                                              1.5                                                                              1.5                                                                               0.5                                                                               1.5                                                                               3   2  0   0   0   2   0   0.5 98  2                   *212                                                                              76.8  2 6.2                                                                              1.5                                                                              0.5                                                                               3  4  1.5 1.5                                                                               0   0   3   0   0   0   99.5                                                                               0.5                 *213                                                                              82.7  2 4 0.3                                                                              1  0  3.5                                                                               2   2.5                                                                               0   2   0   0   0   0   99  1                   *214                                                                              79.8  1.5                                                                              2.5                                                                              4.7                                                                              0  1  4  2   2  0   0   0   2.5 0   0   99  1                   *215                                                                              78.8  2 2.5                                                                              2 2.2                                                                               2  5  2   1.5                                                                               0   0   0   0   2   0   99  1                   *216                                                                              80.7  2.5                                                                              4.5                                                                              1.5                                                                              1  2  3  2   1.3                                                                               0   0   0   0   0   1.5 99.5                                                                               0.5                 *217                                                                              79.3  1.5                                                                              2.5                                                                              1 0  1.5                                                                               4  2.2 4  0   0   0   4   0   0   99  1                   *218                                                                              85.2  1.5                                                                              3 2 1  0  6  1   0  0.3 0   0   0   0   0   99.5                                                                               0.5                 *219                                                                              76.3  1.5                                                                              2.5                                                                              1 3  1  5  0   4  0   0.7 2.5 2.5 0   0   99  1                   *220                                                                              77.5  4 2 4 3  1  3  3   1  0   0   1.5 0   0   0   100 0                    221                                                                              83.5  1.5                                                                              2.5                                                                              1 2  0  3.5                                                                               1   3  0   0   2   0   0   0   97.5                                                                               2.5                 *222                                                                              78    4 2 4 1  0  5  2   2  0   0   2   0   0   0   97.3                                                                               2.7                 __________________________________________________________________________      *indicates out of the scope of the invention                             

                  TABLE 10                                                         ______________________________________                                               main      first by-                                                      Sample                                                                               component component second by-component (wt %)                           No.   (wt %)    (wt %)    Cr   Mn   Fe   Co   Ni                               ______________________________________                                         223   98.99     1.0       0    0.01 0    0    0                                224   98.85     1.0       0.05 0.05 0.05 0    0                                225   98.95     1.0       0    0    0    0.05 0                                226   98.9      1.0       0.05 0    0    0    0.05                             227   98.85     1.0       0    0.1  0    0    0.05                             228   98.65     1.0       0.05 0.2  0.05 0.05 0                                229   98.6      1.0       0    0.3  0    0    0.1                              230   98.55     1.0       0    0.3  0    0.1  0.05                             231   98.5      1.0       0.1  0.3  0    0.1  0                                *232  98.45     1.0       0    0.35 0.05 0.1  0.05                             ______________________________________                                          *indicates out of the scope of the invention                             

                                      TABLE 11                                     __________________________________________________________________________     baking     electronic property mechanical property                             Sample                                                                             temperature    TC (%)                                                                              bias TC (%)                                                                           deflective strength                             No. (°C.)                                                                          ε                                                                         tan δ (%)                                                                     ΔC.sub.max                                                                    ΔC.sub.maxB                                                                     (kg/cm.sup.2)                                   __________________________________________________________________________      201                                                                               1140   2020                                                                              1.4  -12.0                                                                               -32.5  2050                                             202                                                                               1100   1870                                                                              1.5  -13.3                                                                               -32.0  2280                                             203                                                                               1100   1650                                                                              1.7  -14.2                                                                               -32.5  2170                                             204                                                                               1160   1700                                                                              1.3  -11.8                                                                               -31.0  1780                                             205                                                                               1120   1570                                                                              1.2  10.6 -33.0  2210                                             206                                                                               1080   1810                                                                              1.2  -14.2                                                                               -32.5  2200                                             207                                                                               1100   2090                                                                              1.7  -14.5                                                                               -34.0  2090                                             208                                                                               1100   1850                                                                              1.6  12.1 -33.5  2150                                            *209                                                                               1160   1910                                                                              2.0  -17.5                                                                               -32.8  1470                                            *210                                                                               1120   1800                                                                              1.3  -21.4                                                                               -40.5  2020                                            *211                                                                               1120   1780                                                                              1.7  -23.3                                                                               -33.0  1450                                            *212                                                                               1100    970                                                                              1.2  -14.7                                                                               -29.0  2260                                            *213                                                                               1100   2070                                                                              1.7  -23.5                                                                               -40.6  2310                                            *214                                                                               1140   1500                                                                              1.1  -17.0                                                                               -41.0  2010                                            *215                                                                               1140   2000                                                                              1.3  -18.5                                                                               -31.7  1980                                            *216                                                                               1120   1990                                                                              1.4  -18.0                                                                               -32.8  2120                                            *217                                                                               1160   1750                                                                              1.7  -19.5                                                                               -31.5  2050                                            *218                                                                               1160   1800                                                                              1.3  17.5 -40.2  1830                                            *219                                                                               1160   2150                                                                              1.8  20.0 -33.5  2110                                            *220                                                                               1160° C. (not sintered)                                              221                                                                               1080   1400                                                                              1.2  13.5 -31.4  2150                                            *222                                                                               1080    960                                                                              1.1  14.1 -30.4  2140                                            __________________________________________________________________________      indicates out of the scope of the invention                              

                                      TABLE 12                                     __________________________________________________________________________     baking     electronic property mechanical property                             Sample                                                                             temperature    TC (%)                                                                              bias TC (%)                                                                           deflective strength                             No. (°C.)                                                                          ε                                                                         tan δ (%)                                                                     ΔC.sub.max                                                                    ΔC.sub.maxB                                                                     (kg/cm.sup.2)                                   __________________________________________________________________________     223 1120   2010                                                                              1.5  -12.3                                                                               -33.0  2050                                            224 1120   1920                                                                              1.6  -12.0                                                                               -33.3  2020                                            225 1120   2010                                                                              1.5  -12.7                                                                               -33.2  1990                                            226 1120   1980                                                                              1.6  -12.5                                                                               -33.0  2060                                            227 1120   2060                                                                              1.7  -13.1                                                                               -33.0  2050                                            228 1120   1880                                                                              2.0  -12.1                                                                               -33.0  1980                                            229 1120   1920                                                                              2.0  -12.3                                                                               -33.8  1960                                            230 1120   1940                                                                              2.1  -12.5                                                                               -33.5  1950                                            231 1120   1920                                                                              2.1  -12.9                                                                               -33.5  1980                                            *232                                                                               1120   1830                                                                              2.8  -11.8                                                                               -32.2  1990                                            __________________________________________________________________________      *indicates out of the scope of the invention                              

What is claimed is:
 1. A dielectric ceramic composition composed of, 97.5 to 99.95 wt. % of main component represented by a following general formula, {100-(a+b+c+d)}(Ba_(100-x) Pb_(x))TiO₃ +aZnO+bBi₂ O₃ +cNb₂ O₅ +dRe₂ O₃ (where, Re is at least one kind selected from La, Pr, Nd, Sm, Dy and Er, a, b, c, d and x designate mol. %) and are within the following ranges,0.5≦a≦4.5 0.5≦b≦4.5 0.5≦c≦4.5 0.5≦d≦5.50<x≦6.0, and 0.05 to 2.5 wt. % of first by-component consisting of glass whose main component is SiO₂.
 2. A dielectric ceramic composition composed of, 97.0 to 99.94 wt. % of main component represented by a following general formula, {100-(a+b+c+d)}(Ba_(100-x) Pb_(x))TiO₃ +aZnO+bBi₂ O₃ +cNb₂ O₅ +dRe₂ O₃ (where, Re is at least one kind selected from La, Pr, Nd, Sm, Dy and Er, a, b, c, d, and x designate mol. %) and are within the following ranges,0.5≦a≦4.5 0.5≦b≦4.5 0.5≦c≦4.5 0.5≦d≦5.50<x≦6.0,
 0. 05 to 2.5 wt. % of first by-component consisting of glass whose main component is SiO₂, and 0.01 to 0.5 wt. % of second by-component consisting of at least one kind selected from oxides of Cr, Mn, Fe, Co and Ni.
 3. A dielectric ceramic composition composed of, 97.5 to 99.95 wt. % of main component represented by a following general formula, {100-(a+b+c+d+e)}BaTiO₃ +aZnO+bBi₂ O₃ +cMeO₂ +dNb₂ O₅ +eRe₂ O₃ (where, Me is at least one kind selected from Ti, Zr and Sn, Re is at least one kind selected from La, Pr, Nd, Sm, Dy and Er, a, b, c, d and e designate mol. %) and are within the following ranges,0.5≦a≦4.5 2.0≦b≦6.0 0.5≦c≦6.5 0.5≦d≦4.5 0.5≦e≦5.5, and 0.05 to 2.5 wt. % of first by-component consisting of glass whose main component is SiO₂.
 4. A dielectric ceramic composition composed of, 97.0 to 99.94 wt. % of main component represented by a following general formula, {100-(a+b+c+d+e)}BaTiO₃ +aZnO+bBi₂ O₃ +cMeO₂ +dNb₂ O₅ +eRe₂ O₃ (where, Me is at least one kind selected from Ti, Zr, and Sn, Re is at least one kind selected from La, Pr, Nd, Sm, Dy and Er, a, b, c, d and e designate mol. %) and are within the following ranges,
 0. 5≦a≦4.52.0≦b≦6.0 0.5≦c≦6.5 0.5≦d≦4.5 0.5≦e≦5.5, 0.05 to 2.5 wt. % of first by-component consisting of glass whose main component is SiO₂, and 0.01 to 0.5 wt. % second by-component consisting of at least one kind selected from oxides of Cr, Mn, Fe, Co and Ni.
 5. A dielectric ceramic composition composed of, 97.5 to
 99. 95 wt. % of main component represented by a following general formula, {100-(a+b+c+d+e+f)}BaTiO₃ +aZnO+bBi₂ O₃ +cNb₂ O₅ +dMaO+eMbO₂ +fRe₂ O₃ (where, Ma is at least one kind selected from Pb and Ca, Mb is at least one kind selected from Ti, Zr and Sn, Re is at least one kind selected from La, Pr, Nd, Sm, Dy and Er, a, b, c, d, e and f designate mol. %) and are within the following ranges,0.5≦a≦4.5 2.0≦b≦6.0 0.5≦c≦4.5 0<d≦4.0 6.5≦e≦10.0 0.5≦f≦5.5, and 0.05 to 2.5 wt. % of first by-component consisting of glass whose main component is SiO₂.
 6. A dielectric ceramic composition composed of, 97.0 to
 99. 94 wt. % of main component represented by a following general formula, {100-(a+b+c+d+e+f)}BaTiO₂ +aZnO+bBi₂ O₃ +cNb₂ O₅ +dMaO+eMbO₃ +fRe₂ O₃ (where, Ma is at least one kind selected from Pb and Ca, Mb is at least one kind selected from Ti, Zr and Sn, Re is at least one kind selected from La, Pr, Nd, Sm, Dy and Er, a, b, c, d, e and f designate mol. %) and are within the following ranges,0.5≦a≦4.5 2.0≦b≦6.0 0.5≦c≦4.5 0<d≦4.0 6.5≦e≦10.0 0.5≦f≦5.5 0.05 to 2.5 wt. % of first by-component consisting of glass whose main component is SiO₂, and 0.01 to 0.5 wt. % of second by-component consisting of at least one kind selected from oxides of cr, Mn, Fe, Co and Ni. 